Tetrahydrofuran → 1-bromo-4-(phenylethynyl)benzene

HRID 1670356Notes

Reaction equation

HRID 1670356 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[C:9]1([C:15]#[CH:16])[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.O1CCCC1.[O-][Si]([O-])=O.[Mg+2]>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.[Cu]I.C(N(CC)CC)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:16]#[C:15][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 8028TetrahydrofuranHCID 10821PhenylacetyleneHCID 115221-Bromo-4-iodobenzeneHCID 61680MAGNESIUM SILICATE (synthetic)

Product 1

HCID 2908881-bromo-4-(phenylethynyl)benzeneYield 58.3%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Procedure

Into a 1000-mL three-neck flask were added 28.3 g (0.10 mol) of p-bromoiodobenzene, 10.2 g (0.10 mol) of phenylacetylene, 701 mg (1 mmol) of bis(triphenylphosphine)palladium(II)dichloride, and 190 mg (1 mmol) of copper(I) iodide, and nitrogen substitution was carried out. Then, 350 mL of tetrahydrofuran and 18 mL of triethylamine were added thereto, and the mixture was stirred at room temperature for 12 hours. After the reaction, the reaction mixture was washed with a 3% hydrochloric acid aqueous solution, and an aqueous phase was extracted with ethyl acetate. The extract combined with an organic phase was washed with a saturated saline solution and then dried with magnesium sulfate. The mixture was filtered through Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855, the same product was used hereinafter), Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135, the same product was used hereinafter), and alumina, and a solid obtained by the concentration of the filtrate was recrystallized with hexane to give 15 g of the target product as a solid at a yield of 58%.

Workup

  1. customAfter the reaction
  2. washthe reaction mixture was washed with a 3% hydrochloric acid aqueous solution
  3. extractionan aqueous phase was extracted with ethyl acetate
  4. washwas washed with a saturated saline solution
  5. dry with materialdried with magnesium sulfate
  6. filtrationThe mixture was filtered through Celite (
  7. customproduced by Wako Pure Chemical Industries, Ltd
  8. customproduced by Wako Pure Chemical Industries, Ltd
  9. customa solid obtained by the concentration of the filtrate
  10. customwas recrystallized with hexane

Sources & evidence

ORD record
ord-fc69b0f503e949c1b9c18435bd0e4f27
Source dataset
uspto-grants-2011_08
Patent number
US07993761B2

Reaction notes

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